WO2007069521A1 - Copolymère bloc et produit hydrogéné à partir dudit copolymère - Google Patents

Copolymère bloc et produit hydrogéné à partir dudit copolymère Download PDF

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WO2007069521A1
WO2007069521A1 PCT/JP2006/324432 JP2006324432W WO2007069521A1 WO 2007069521 A1 WO2007069521 A1 WO 2007069521A1 JP 2006324432 W JP2006324432 W JP 2006324432W WO 2007069521 A1 WO2007069521 A1 WO 2007069521A1
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Prior art keywords
block copolymer
group
block
polymer block
styrene
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PCT/JP2006/324432
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English (en)
Japanese (ja)
Inventor
Kenji Suzuki
Kenji Shachi
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Kuraray Co., Ltd.
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Priority to CA2631293A priority Critical patent/CA2631293C/fr
Priority to ES06834187T priority patent/ES2710878T3/es
Priority to JP2007550149A priority patent/JP5263480B2/ja
Priority to EP06834187.4A priority patent/EP1961778B1/fr
Priority to US12/096,105 priority patent/US20090270556A1/en
Priority to CN2006800468513A priority patent/CN101331162B/zh
Publication of WO2007069521A1 publication Critical patent/WO2007069521A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the present invention relates to an aromatic vinyl compound block copolymer and a hydrogenated product thereof.
  • aromatic vinyl compound block copolymers have been used in various resin modifiers, adhesives, and the like, taking advantage of their excellent flexibility and adhesiveness.
  • aromatic bur compound block copolymers are nonpolar and nonreactive themselves, they are generally compatible with nonpolar materials such as polyolefins, polystyrenes, petroleum softeners such as process oils, etc.
  • resins such as engineering plastics and polar materials such as inorganic compounds.
  • engineering plastics have much better heat resistance than aromatic vinyl-ic compound block copolymers, so aromatic vinyl-ic compound block copolymers are added as modifiers. In such a case, there is a problem that the heat resistance is lowered. For this reason, it is desired to impart polarity, reactivity and heat resistance to the aromatic bur compound block copolymer.
  • a method of introducing a functional group into a polymer a method of introducing a carboxyl group at the terminal by reacting the active terminal of isoprene with a carbon salt, a metal salt of monochloroacetic acid, etc.
  • a method of introducing a carboxyl group at the terminal by reacting the active terminal of isoprene with a carbon salt, a metal salt of monochloroacetic acid, etc. See Non-Patent Document 1
  • an aromatic vinyl compound block copolymer and an unsaturated carboxylic acid or derivative thereof are reacted in the presence of a radical initiator in an extruder to form a functionalized block copolymer.
  • a manufacturing method see Patent Documents 1 and 2) has been proposed.
  • Non-Patent Document 1 does not describe an example in which carboxyl is actually introduced into an aromatic vinyl compound block copolymer, and the carboxyl group introduced by this method is not described. Since the position is limited to the terminal and a large number of carboxyl groups cannot be introduced, the effect of imparting polarity is small and there is almost no effect of imparting heat resistance. Also, In the methods of Patent Documents 1 and 2, although polarity is imparted, the introduction site of the functional group is limited to the aliphatic chain, so that sufficient heat resistance is not exhibited.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 63-254119
  • Patent Document 2 Japanese Patent Application Laid-Open No. 64-79212
  • Non-Patent Document 1 European Polymer Journal (Eur.Polym.J.), 1992, 28 ⁇ , 7, p765
  • an object of the present invention is to provide an aromatic bur compound block copolymer having polarity, reactivity and heat resistance.
  • [1] Mainly composed of an aromatic bur compound unit, and the aromatic bul compound unit has an alkyl group having at least one functional group selected from a force lpoxyl group and a group derived from the force bonded to a benzene ring.
  • the aromatic vinyl compound unit is conjugated with a polymer block A containing a styrene unit having an alkyl group bonded to a benzene ring.
  • block copolymer (I) To hydrogenated products (hereinafter collectively referred to as “block copolymer (I)”)
  • the hard block has a styrene unit in which an alkyl group having at least one functional group selected from a carboxyl group and a group derived from the carboxyl group is bonded to a benzene ring.
  • a thermoplastic elastomer aromatic bur compound block copolymer having reactivity and excellent heat resistance (for example, tensile permanent elongation at 70 ° C.) is provided.
  • the block copolymer of the present invention or a hydrogenated product thereof is mainly composed of an aromatic bull compound unit, and the aromatic bull compound unit is at least one functional group selected from a carboxyl group and a group derived from the carboxyl group.
  • a polymer or a hydrogenated product thereof hereinafter, these may be collectively referred to as “modified block copolymer (I)”), and the block copolymer (I) has a functional group.
  • Units include, for example, styrene; monomethyl styrene; ⁇ -methyl styrene; o_alkynol styrene, m-alkyl styrene, p-alkyl styrene, 2, 4-dialkyl styrene, 3, 5-dialkyl styrene, 2, 4 , 6-trialkylstyrene or the like alkyl styrene having an alkyl group bonded to the benzene ring; halogen styrene having one or more hydrogen atoms of the alkyl group in the alkyl styrene substituted with a halogen atom ; Halogenated styrene such as monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene; methoxystyrene, binaphthalene, vinyl anthracene, etc.
  • an alkyl group with an alkyl group attached to the benzene ring Styrene, halogenated alkyl styrene (hereinafter les, U) a force even Shi preferred are units derived les.
  • an alkylstyrene unit in which an alkyl group having an alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring is preferred.
  • the p-methylstyrene unit is preferable as the alkylstyrene unit because it is easily available.
  • the polymer block A is a thermoplastic elastomer core.
  • the alkyl group bonded to the benzene ring in the alkylstyrene unit has a role of introducing a functional group into the hard segment of the block copolymer.
  • the ratio of the alkylstyrene unit in the polymer block A is determined by the block copolymer (I)
  • All units may be alkylstyrene units. If the proportion of the alkylstyrene unit is less than 1% by mass, the functional group is not sufficiently introduced into the polymer block A,
  • the resulting block copolymer does not show sufficient reactivity.
  • the bonding form of the alkylstyrene unit and the other aromatic vinyl compound unit in the polymer block A may be any form such as random, block, and tapered.
  • the content of the polymer block A in the block copolymer (I) is in the range of 10 to 40% by mass. It is preferably within the range. When the content is less than 10% by mass, the cohesiveness and reactivity of the hard block, which is the polymer block A force, are reduced, and the resulting modified block co-polymer
  • Polymer block A is an aromatic bur compound unit containing an alkylstyrene unit.
  • the ratio of the other polymerizable monomer force-derived units is determined by the block copolymer (I).
  • polymerizable monomers More preferably, it is 10 mass% or less.
  • examples of other polymerizable monomers in that case include butadiene and isoprene.
  • conjugated gen examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentagen, and 1,3-hexagen.
  • Polymer block B may be composed of only one of these conjugation force-induced units, or it may be composed of two or more forces. Of these, butadiene, isoprene or a mixture of butadiene and isoprene is preferred to be composed of units that are induced. There are no particular restrictions on the type and content of the microstructure of polymer block B.
  • binding form can be random, block, tapered, or a combination of two or more thereof.
  • the polymer block B may be another polymerizable monomer, if necessary, together with a conjugated diene unit.
  • the proportion of other polymerizable monomer units is determined by the mass of the polymer block B constituting the block copolymer (I) [block copolymer weight].
  • the content is preferably 0% by mass or less, more preferably 10% by mass or less.
  • examples of other polymerizable monomers include styrene, monomethylstyrene, and the above-described alkylstyrene (preferably P-methylstyrene) constituting an alkylstyrene unit.
  • the polymer block B is a polyisoprene block composed of isoprene units or the isoprene block.
  • Hydrogenated polyisoprene block in which some or all of the carbon-carbon double bonds based on the ren units are hydrogenated; Polybutadiene block that has a butadiene unit strength or some or all of the carbon-carbon double bonds based on the butadiene units Hydrogenated polybutadiene block in which isoprene units and isoprene units consisting of isoprene units and butadiene units. Butadiene copolymer blocks or carbon-carbon double bonds based on the isoprene units and butadiene units are partially or fully hydrogenated. A hydrogenated isoprene butadiene copolymer block is preferred.
  • the block copolymer (I) is used as long as the polymer block A and the polymer block B are bonded.
  • the bond form is not limited and may be linear, branched, radial, or a combination of two or more of them. Among them, polymer block A
  • the bond form between 0 and polymer block B is preferably linear.
  • Examples thereof include a block copolymer, a tetrablock copolymer represented by A—B—A—B, and a pentablock copolymer represented by A—B—A—B A.
  • the triblock copolymer (A—B—A) is easy and flexible to produce the block copolymer (I).
  • the number average molecular weight of the block copolymer (I) is not particularly limited, but is preferably 30000.
  • the number average molecular weight here means the number average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).
  • the block copolymer (I) is produced, for example, by the following known anion polymerization method.
  • alkyl styrene or an aromatic butyl derived from alkyl styrene is derived from an alkyl lithium compound in an organic solvent inert to the polymerization reaction such as n_hexane or cyclohexane.
  • a block copolymer (that is, an unhydrogenated block copolymer (I)) can be produced by sequentially polymerizing a mixture with a compound and conjugated gen.
  • the obtained non-hydrogenated block copolymer is further hydrogenated as necessary.
  • a saturated hydrocarbon solvent such as cyclohexane, Raney nickel; metals such as Pt , pd, R U , Rh, Ni, etc. are carbon, alumina, diatomaceous earth, etc.
  • a catalyst of the Teedala family a metal complex consisting of a combination of a bis (cyclopentadienyl) compound of a transition metal such as titanium, zirconium or hafnium, and an organometallic compound such as lithium, sodium, potassium, ananolium, zinc or magnesium.
  • reaction temperature is usually 20-100 ° C
  • Elementary pressure 0.1 ⁇ It can be performed under the condition of OMPa, and it is possible to obtain a hydrogenated product of the block copolymer (that is, a hydrogenated block copolymer (I)). .
  • the hydrogenation rate can be appropriately adjusted according to the physical properties required for the modified block copolymer of the present invention. However, with emphasis on heat resistance and the like, introduction of functional groups into the polymer block A is important. Amount
  • the hydrogenation rate is more preferably 95% or more, more preferably 90% or more.
  • the hydrogenation rate of the carbon-carbon double bond based on the conjugation unit of polymer block B is determined based on the polymer block before and after the hydrogenation reaction by measuring means such as iodine titration, infrared spectrophotometer, and nuclear magnetic resonance. Measure the amount of carbon-carbon double bonds in B
  • the block copolymer (I) is selected from a carboxyl group and a group derived from the carboxyl group
  • the modified block copolymer (1) By adding an unsaturated compound having at least one functional group (compound having a carbon-carbon double bond), the modified block copolymer (1), that is, mainly composed of aromatic vinyl compound units,
  • the aromatic bur compound unit is conjugated with a polymer block A containing a styrene unit in which an alkyl group having at least one functional group selected from a carboxynole group and a group derived from the carboxylene group is bonded to a benzene ring.
  • the functional group include a carboxyl group, a salt thereof, an ester group, and an amide.
  • the unsaturated compound having a functional group examples include maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid, and unsaturated carboxylic acids such as cis-1-cyclohexene-1,2-dicarboxylic acid; And salts such as metal salts, esters and amides; acid anhydrides such as maleic anhydride; maleimides and the like.
  • maleic anhydride which is easily available and excellent in reactivity, is particularly preferable.
  • One type of unsaturated compound having a functional group may be used alone, or two or more types may be used in combination.
  • modified block copolymer (I) may be cross-linked.
  • the crosslinked modified block copolymer (I) can be produced by the following method. For example, an acid anhydride such as maleic anhydride or maleimide was added to the block copolymer (I) in the same manner as described above.
  • the alkyl group having a functional group contained in the polymer block A of the modified block copolymer (I) is added to the benzene ring.
  • Bonded styrene units (hereinafter sometimes referred to as “functionalized alkylstyrene units”) are formed.
  • the content of the functionalized alkyl styrene unit in the block copolymer (I) is preferably in the range of 2.0 to 50 monolayers with respect to 1 mole of the block copolymer (1). Within the range of moles is more preferred Within the range of 3 to 25 moles is even more preferred. If the content is less than 2.0 mol, it is difficult for the modified block copolymer (I) to improve the heat resistance and the like of the block copolymer (I), while the content is less than 50 mol.
  • the content of the functionalized alkylstyrene unit in the polymer block A can be measured by a nuclear magnetic resonance method. That is, the number of protons on carbon, which is the reaction point in polymer block A in the addition reaction of unsaturated compounds having functional groups, is measured before and after the reaction, and calculated from the amount of change.
  • the content of the functionalized alkylstyrene unit in the polymer block A can also be determined by acid value titration, infrared spectrophotometer or the like.
  • radical initiators include ⁇ , ⁇ ′-di (t-butylperoxy) diisopropylbenzene, 2,5 dimethyl-2,5 di (tert-butylenoperoxy) hexane, 2,5 dimethyl-2,5-bis (t-butylperoxy) Hexin-1, Dicumyl peroxide, n_Butyl 4, 4-di (t_butyl peroxide) valley, Di_t_Butyl peroxide, Di-t-hexyloxide, t-Butylhydroxyperoxide, Examples thereof include 1,1-di (t_butylperoxy) cyclohexane, dibenzoyl peroxide, dilauryl peroxide, peracetic acid, hydrogen peroxide, and the like.
  • di- (t_butylperoxy) diisopropylbenzene and 2,5-dimethyl-1,2-di (t_butylperoxy) hexane are preferable.
  • One radical initiator may be used alone, or two or more radical initiators may be used in combination.
  • an unsaturated compound having a functional group can be added to the block copolymer (I) by irradiation with active energy rays.
  • the Active energy rays include particle rays, electromagnetic waves, and combinations thereof.
  • particle beams include electron beams (EB) and strands
  • electromagnetic waves include ultraviolet rays (UV), visible rays, infrared rays, ⁇ rays, and X rays.
  • UV ultraviolet rays
  • visible rays visible rays
  • infrared rays ⁇ rays
  • X rays X rays
  • a photopolymerization initiator such as benzophenone.
  • an acceleration voltage of 0.1 to 10 MeV is appropriate, and an irradiation dose in the range of l to 500 kGy is appropriate.
  • a lamp having a radiation wavelength of 200 nm to 450 nm can be suitably used as the radiation source.
  • the radiation source include a tungsten filament in the case of an electron beam, and examples include a low pressure mercury lamp, a high pressure mercury lamp, an ultraviolet mercury lamp, a carbon arc lamp, a xenon lamp, and a zirconium lamp.
  • modified block copolymer (I) of the present invention include, for example, the following methods.
  • block copolymer (I) is added to cyclohexane, methylsilane under nitrogen atmosphere.
  • Block copolymer (I) and unsaturated compound with functional group are dissolved in organic solvent such as toluene.
  • the modified block copolymer (I) of the present invention can be used as a modifier of the flexibility, impact resistance, and heat resistance of a thermoplastic resin.
  • thermoplastic resin to be modified include homopolymers such as polyethylene and polypropylene; ethylene monopropylene copolymer, ethylene 1-butene copolymer, ethylene 1-hexene copolymer, and ethylene 1-one.
  • Ethylene ⁇ -olefin copolymers such as pentene copolymer, ethylene 1-octene copolymer; Polyolefins such as ethylene acetate butyl copolymer, ethylene acrylate copolymer, ethylene-methacrylate copolymer Polystyrene resins; Styrene resins such as polystyrene, acrylonitrile monostyrene resins, acrylonitrile monobutadiene styrene resins; Atalinole resins such as polyacrylate resins and polymethacrylate copolymers; Polyphenylene ether resins; Poly Methylene ether resin; Polycarbonate resin ; Polyvinyl chloride resin; Polyvinyl acetate resin; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid, poly force prolatatone, polyamide 6, polyamide 6 ⁇ 6, polyamide 6 ⁇ 10, polyamide 11, polyamide
  • an inorganic filler can be added for the purpose of imparting heat resistance, imparting flame retardancy, reinforcing rigidity, filling and the like.
  • inorganic fillers include talc, glass fiber, my strength, kaolin, clay, calcium silicate, glass, glass hollow sphere, calcium carbonate, magnesium carbonate, aluminum hydroxide, and magnesium hydroxide.
  • a softener can be added to the modified block copolymer (I) of the present invention as required.
  • Softening agents include petroleum softeners such as paraffinic, naphthenic and aromatic process oils and vegetable oil softeners such as paraffin, peanut oil and rosin. These softening agents can be used alone or in combination of two or more.
  • the amount of the softening agent is not particularly limited as long as the gist of the present invention is not impaired, but is usually 300 parts by mass or less with respect to 100 parts by mass of the modified block copolymer (I), preferably 100 quality. It is below the amount part.
  • the modified block copolymer (I) of the present invention includes other polymers such as natural rubber and synthetic compounds for the purpose of modifying flexibility, fluidity and the like within the range not impairing the gist of the present invention.
  • the modified block copolymer (I) of the present invention includes, for example, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, and a colorant within the range not impairing the gist of the present invention.
  • Other additives such as antistatic agents, flame retardants, foaming agents, water repellents, waterproofing agents, tackifiers, fluorescent agents, antiblocking agents, metal deactivators and antibacterial agents may be added. ,.
  • the modified block copolymers or block copolymers obtained in the examples or comparative examples were pressed for 3 minutes at 230 ° C and lOMPa, and 15 cm X 15 cm X 0 A 1 cm sheet was prepared.
  • a specimen of dumbbell No. 5 was prepared from the obtained sheet, and a tensile test was performed at a tensile speed of 500 mmZmin at a temperature of 23 ° C using an Instron universal testing machine. The elongation at break (%) was measured.
  • a reaction mixture containing poly (p-methylenostyrene) -polybutadiene-poly (p-methylstyrene) triblock copolymer was obtained.
  • the number average molecular weight of the obtained block copolymer was 87000, and the content of ⁇ -methylstyrene unit measured by “ ⁇ - ⁇ R” was 30% by mass.
  • a hydrogenation catalyst prepared from nickel octylate (64% by mass, cyclohexane solution) 56g and triisopropylaluminum (20% by mass, cyclohexane solution) 380g was added to the reaction mixture containing the block copolymer.
  • a hydrogenation reaction was performed, and the hydrogenated product of the above-mentioned poly (p-methylstyrene) polybutadiene / poly (p-methylstyrene) triblock copolymer (hereinafter referred to as “block copolymer I”
  • the number average molecular weight of the resulting block copolymer I-1 was 90000.
  • Cylberoxy) diisopropylbenzene (10 g) was mixed, melt kneaded at 230 ° C using a twin screw extruder, dissolved in THF, reprecipitated with methanol, and poly (p-methylstyrene-polybutadiene-poly p-methylstyrene).
  • a maleic acid derivative-modified product of a hydrogenated product of a triblock copolymer hereinafter referred to as “modified block copolymer I-1” was obtained.
  • the acid value of the resulting modified block copolymer I_1 was 10 (mgZg), and 10 maleic anhydrides were added per molecule of the modified block copolymer 1-1.
  • modified block copolymer I 1 obtained in Example 1 was dissolved in THF, and 0.5 parts by mass of magnesium hydroxide was added to the modified block copolymer I 1 and re-added with methanol.
  • a magnesium salt of a modified maleic acid derivative of a hydrogenated poly p-methylstyrene polybutadiene poly p-methylstyrene triblock copolymer (hereinafter referred to as “modified block copolymer 1-2”). Obtained).
  • modified block copolymer 1-2 a modified maleic acid derivative of a hydrogenated poly p-methylstyrene polybutadiene poly p-methylstyrene triblock copolymer
  • Block copolymer I-1 obtained in Example 1 10 kg, maleic anhydride 200 g, a, a ′ o
  • modified block copolymer I-3 A hydrogenated maleic acid derivative-modified product (hereinafter referred to as “modified block copolymer I-3”) was obtained.
  • the acid value of the resulting modified block copolymer I-13 is 2 O (mgZg), which means that 20 maleic anhydrides were added per molecule of the modified block copolymer 1_3.
  • 6 mol% of protons in the p_methyl group are shifted to a low magnetic field, and 8 maleic anhydrides per molecule of the modified block copolymer 1_ 3 are attached to the polymer block A. It will be done.
  • the above-described physical properties were evaluated using the modified block copolymer 1-3. The results are shown in Table 1.
  • modified block copolymer 1_3 obtained in Example 3 was dissolved in THF, 1.0 part by mass of magnesium hydroxide was added to the modified block copolymer 1_3, and reprecipitated with methanol.
  • Magnesium salt of a modified maleic acid derivative of a hydrogenated poly (p-methylstyrene-polybutadiene-poly (p-methylstyrene) triblock copolymer (hereinafter referred to as “modified block copolymer 1-4”) Got.
  • modified block copolymer 1-4 the physical properties described above were evaluated. The results are shown in Table 1.
  • Block copolymer I-1 obtained in Example 1 4 kg, maleic anhydride 40 g, a, a ' ⁇ ⁇
  • Di (t-butylperoxy) diisopropylbenzene 3 ⁇ 2g was mixed, melt-kneaded at 230 ° C using a twin screw extruder, dissolved in THF, reprecipitated with methanol, poly (p-methylstyrene) polybutadiene
  • a hydrogenated product of poly p-methylstyrene triblock copolymer was modified with a maleic acid derivative (hereinafter referred to as “modified block copolymer I-15”).
  • the acid value of the obtained modified block copolymer 1-1 was 3 (mg / g), and three maleic anhydrides were added per molecule of the modified block copolymer 1-5.
  • modified block copolymer I5 obtained in Example 5 was dissolved in THF, and 0.15 parts by mass of magnesium hydroxide was further added to the modified block copolymer I5, followed by reprecipitation treatment with methanol.
  • the magnesium salt of a modified maleic acid derivative of a hydrogenated product of poly (p-methylstyrene-polybutadiene-poly (p-methylstyrene) triblock copolymer (hereinafter referred to as “modified block copolymer 1_6”). Obtained).
  • modified block copolymer 1_6 modified maleic acid derivative of a hydrogenated product of poly (p-methylstyrene-polybutadiene-poly (p-methylstyrene) triblock copolymer
  • reaction mixture containing polystyrene-polybutadiene-polystyrene triblock copolymer.
  • the number average molecular weight of the obtained block copolymer was 87000, and the content of styrene units measured by NMR was 30% by mass.
  • block copolymer 1 To the reaction mixture containing the block copolymer, Okuchiru acid nickel (64 wt%, hexane solution consequent opening) 56 g and triisopropyl aluminum hydrogenation catalyst prepared from 380 g (20 mass 0/0, hexane solution cyclo) Then, hydrogenation reaction was carried out in a hydrogen atmosphere of 80 ° C and IMPa, and the hydrogenated product of the above-mentioned polystyrene polybutadiene polystyrene triblock copolymer (hereinafter referred to as "block copolymer 1") Got.
  • the number average molecular weight of the obtained block copolymer 1 was 90,000, and the content of styrene units and the hydrogenation rate measured by 1 H NMR were 29% by mass and 97 respectively. /. It was.
  • modified block copolymer 1 10 kg of block copolymer, 200 g of maleic anhydride, 10 g of di-, di- (t-butylbaroxy) diisopropylbenzene were mixed and melt-kneaded at 230 ° C using a twin screw extruder. Dissolved in THF, reprecipitated with methanol, modified maleic acid derivative of hydrogenated product of polystyrene-polybutadiene-polystyrene triblock copolymer ( This is hereinafter referred to as “modified block copolymer 1”).
  • the acid value of the obtained modified block copolymer 1 is 10 (mg / g), and 10 maleic anhydrides are added per molecule of the block copolymer.
  • the modified block copolymer 1 the above-mentioned physical properties were evaluated. The results are shown in Table 2.
  • modified block copolymer 1 obtained in Comparative Example 1 was dissolved in THF, and 0.5 parts by mass of magnesium hydroxide was added to the modified block copolymer 1 and reprecipitated with methanol.
  • a magnesium salt of a maleic acid derivative modified product of a hydrogenated product of polystyrene / polybutadiene / polystyrene triblock copolymer (hereinafter referred to as “modified block copolymer 2”) was obtained.
  • modified block copolymer 2 was obtained using the modified block copolymer 2, the above physical properties were evaluated. The results are shown in Table 2.
  • test piece broke during the elongation of the test piece.
  • the modified block copolymers I 1 to 16 obtained in 1 to 6 are the modified permanent block copolymer 1, the modified block copolymer 2, and the block copolymer I 1 that have a small tensile permanent elongation at 70 ° C.
  • the modified block copolymer of the present invention can be used as a polar resin modifier, an inorganic filler dispersibility improver, etc. by utilizing its polarity, reactivity and heat resistance.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un copolymère bloc incluant un bloc polymère A et un bloc polymère B. Le bloc polymère A est principalement composé d'un motif vinylaromatique, et le motif vinylaromatique contient un motif styrène où un groupement alkyle, qui comprend au moins un groupement fonctionnel sélectionné dans le groupe constitué par un groupement carboxy et des groupements dérivés dudit groupement carboxy, est lié à un cycle benzénique. Le bloc polymère B est principalement composé d'un motif diène conjugué. La présente invention concerne également un produit hydrogéné obtenu à partir d'un tel copolymère bloc.
PCT/JP2006/324432 2005-12-14 2006-12-07 Copolymère bloc et produit hydrogéné à partir dudit copolymère WO2007069521A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA2631293A CA2631293C (fr) 2005-12-14 2006-12-07 Copolymere bloc et produit hydrogene a partir dudit copolymere
ES06834187T ES2710878T3 (es) 2005-12-14 2006-12-07 Copolímero de bloques y producto hidrogenado del mismo
JP2007550149A JP5263480B2 (ja) 2005-12-14 2006-12-07 ブロック共重合体およびその水素添加物
EP06834187.4A EP1961778B1 (fr) 2005-12-14 2006-12-07 Copolymère bloc et produit hydrogéné à partir dudit copolymère
US12/096,105 US20090270556A1 (en) 2005-12-14 2006-12-07 Block copolymer and hydrogenated product thereof
CN2006800468513A CN101331162B (zh) 2005-12-14 2006-12-07 嵌段共聚物及其氢化物

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JP2005-359763 2005-12-14
JP2005359763 2005-12-14

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WO2007069521A1 true WO2007069521A1 (fr) 2007-06-21

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EP (1) EP1961778B1 (fr)
JP (1) JP5263480B2 (fr)
KR (1) KR20080080543A (fr)
CN (1) CN101331162B (fr)
CA (1) CA2631293C (fr)
ES (1) ES2710878T3 (fr)
WO (1) WO2007069521A1 (fr)

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WO2013073700A1 (fr) * 2011-11-17 2013-05-23 学校法人日本大学 Nouvel ionomère
JPWO2017135177A1 (ja) * 2016-02-02 2018-11-29 日本ゼオン株式会社 酸無水物基を有するブロック共重合体水素化物及びその利用
WO2019044660A1 (fr) * 2017-08-31 2019-03-07 日本ゼオン株式会社 Composition de copolymère à blocs multiples obtenue par traitement de modification, et film

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US7847024B2 (en) * 2007-02-23 2010-12-07 Teknor Apex Company Elastomer and vulcanizate compositions having desirable high temperature properties
CN102702456B (zh) * 2012-06-26 2013-10-23 山东聚圣科技有限公司 一种线型苯乙烯类热塑性弹性体的制备方法
WO2014030573A1 (fr) * 2012-08-23 2014-02-27 株式会社クラレ Film de polyélectrolyte
JP7071968B2 (ja) 2017-05-11 2022-05-19 日本ゼオン株式会社 変性処理により得られるブロック共重合体組成物及びその製造方法、並びにそれに用いられる変性ブロック共重合体組成物及びその製造方法

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WO2013073700A1 (fr) * 2011-11-17 2013-05-23 学校法人日本大学 Nouvel ionomère
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JPWO2017135177A1 (ja) * 2016-02-02 2018-11-29 日本ゼオン株式会社 酸無水物基を有するブロック共重合体水素化物及びその利用
WO2019044660A1 (fr) * 2017-08-31 2019-03-07 日本ゼオン株式会社 Composition de copolymère à blocs multiples obtenue par traitement de modification, et film
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CA2631293A1 (fr) 2007-06-21
CA2631293C (fr) 2013-07-23
US20090270556A1 (en) 2009-10-29
CN101331162A (zh) 2008-12-24
EP1961778A4 (fr) 2009-06-24
JPWO2007069521A1 (ja) 2009-05-21
KR20080080543A (ko) 2008-09-04
JP5263480B2 (ja) 2013-08-14
ES2710878T3 (es) 2019-04-29
CN101331162B (zh) 2012-11-28
EP1961778A1 (fr) 2008-08-27
EP1961778B1 (fr) 2018-12-05

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